Process for the production of water-



United States Patent ,Ofiice g f-$1 112:

3,071,428 wherein X represents a nitrogen atom, which is a mem- PROCESSFOR THE PRODUCTION OF WATER ber of a heterocyclic ring, and couplingcomponents ghggg AZGDYESTUFFS which are free from groups impartingsolubility in Water Richard Gross, Frankfufi am Main, and Werner Kirst 5and couple in a position adjacent to the hyd-roxy group,

and Reinhard Mohr, Offenbach (Main), Germany, a to an alkalineafter-treatment in the presence of a dissignors to Farbwerke HoechstAktiengesellschaft vorpersing agent or a detergent, a compound yieldingmetal mals Meister Lucius & Briining, Frankfurt am Main, and a compoundforming complexes fig ggi g ggii gz ifiggi g N0 81 As azo-dyestuflswhich according to the present inven- Claims Priority, application h aI'm]. i tion can be converted into their complex metal com- 3 Claims (CL3 42) pounds there may be used those which contain in the molecule theou in The present invention relates to the production of I gr p gmetalliferous, water-insoluble azo-dyestufis 0n the fiber.

N N :P-tt N V H OH e N N and N N 3v Q OH OH U.S. Patent No. 2,768,053describes a process for the wherein A represents a heterocyclic ring.These dyeproduction of metalliferous water-insoluble azo-dyestufisstuits are obtained by coupling the diazonium compounds on the fiber,wherein the fiber material, dyed with waterof heterocyclic aminescontaining in the molecule the insoluble azo-dyestuffs containing groupsin o.0'-posi groupings I, II or III described above with coupling tionto the azo-bridge capable of forming metal cOmcomponents containing nogroups imparting solubility in plexes, is after-treated in a bath givingan alkaline re- 40 water, for example sulfonic acid or carboxylic acidaction and containing, besides soap, a salt or hydroxide groups, andcoupling in a'position adjacent to a hydroxy of copper, nickel or cobaltcapable of forming complexes group. and an aliphatic amino orhydroxycatrboxylic acid. In As coupling components there are usedcompounds this process there are used especially those dyestuffscoupling in a position adjacent to a hydroxy group, parwhich areobtained by coupling diazotized o-hydroxyticularly arylamides ofaromatic or heterocyclic o-hyor o-methoxy-amines of the benzene serieswith coudroxycarboxylic acids or acylacetic acids and other aroplingcomponents of the ice color series, i.e. contain a matic or heterocyclichydroxy compounds and como.o'-dihydroxy or o-hydroxy-o'-methoxy azogrouping. pounds containing an enolizable or enolized ketomethyl- Thedyeings obtained according to this process possess ene group in a'heterocyclic ring. Such compounds are, better properties of fastness tolight and chlorine than f r p awlanfides of y yp acid the non-metallizeddyeings. or its derivatives substituted in 6-position, arylamides ofThis invention is based on the observation that valu-2-11Ydr0XY-9I1thTaeI1e-3'carbolq/lic acid, Cresctinic acids,

a'ble water-insoluble metalliferous azo-dyestuffs can be halogenSalicylic acids, Y Y P y -3-carhoXy produced on the fiber by subjectingthe dyeings and acid, Y Y Y C acid, Y Y- printings obtained on the fib fo diazonium- 5 1.2.1'.2'-benzocarbazole-4-carboxylic acid,.3-hydroxy-dipounds of heterocyclic amines containing in the molevPhenylene oxide'z'carboxync acid, 3'hydmxy'diphenyl cule the groupingene sulfide-Z-carboxylic acid, acetoacetic acid, benzoyl- Nm (1) aceticacid or terephthaloyl-bis-acetic acid; hydroXy-ben- I zenes substitutedin p-position for example, 4-chloro-1- hydroxybenzene, '4-methyl- 1-hydroxy-benzene, 4-isopropyl-l-hydroxybenzene,4-tert.-butyl-l-hydroxybenzene,

I (H) 4-acyl-amino-l-hydroxybenzene or 3-amino-4-methyl-1- or C=N-X=hydroxybenzene; polyhydroxybenzenes, for example, 1.3- NH Xdihydroxybenzene, 1.3.5-trihydroxybenzene, 2.4-dihydrox- I 1ybenzophenone or 1.4-di-(2.4-dihydroxybenzoyl)-ben- =o-0-0 zene,hydroxynaphthalenes, for example Z-hydroxynaphll thalene,6-bromo-2Phydroxynaphthalene, 6-methoxy-2-hydroxynaphthalene,7-methoxy-2-hydroxynaphthalene,1-acylamino-7-hydroxy-naphthalene, -chloro-1-hydroxynaphthalene,4-chloro-l-hydroxynaphthalene, 5.8-dichloro-lhydroxynaphthalene,1-acylamino-7-hydroxynaphthalene, 7-benzoylamino-2-hydroxy-naphthalene,l-hydroxynaphthalene-S-sulfonic acid amide,1-hydroxy-4-methoxynaphthalene, 1-hydroxy-4-benzoylnaphthalene,2-hydroxynaphthalene-3-carboxylic acid methyl ester, 2-hydroxynaphthalene-6-carboxylic acid arylamides, Z-hydroxynaphthalene- 6-sulfonic acidamides or Z-hydroxynaphthalene-fi-alkylsulfones, dihydroxynaphthalenes,for example, 1.3-, 2.6- or 2.7-dihydroxynaphthalene, pyrazolones, forexample 1- phenyl-5-pyrazolone-3-carboxylic acid amides, l-phenyl-3-methyl-5-pyrazolone, 1-(4-chlorophenyl)-3-methyl-5- pyrazolone,1-(2'.5-dichlorophenyl)-3-methyl-pyrazolone orl-(naphthyl-Z')-3-methyl-5-pyrazolone or derivatives of barbituric acid.

As heterocyclic amines containing in the molecule the above groupings I,II and III there may be mentioned, for example,2-(2'-aminoaryl)-4.5-arylene-l.2.3-triazole, 2-(2'-aminoaryl) 4.5arylene 1.2.3 triazole-l-oxide, 8 aminoquinoline, 7 aminoindazoles,3-aminoindazoles, 7-aminobenzimidazoles, 7-aminobenztriazoles,l-aminocarbazoles, 2-(2'-aminophenyl)-benzimidazoles, 2-(2'-aminophenyl)-benzthiazoles, 1 (2' aminoaryl)-1.2.3.4- tetrazoles,5-(2-aminoaryl) 1.2.3.4 tetrazoles, 2-(2- aminoaryl) 1.3.4 triazoles,2-(2'-aminoaryl)-1.3.4-=oxdiazole, 2-(2'-aminoaryl)-1.3.4-thiodiazoles,4-aminobenzo- 2.1.3-thiodiazoles and3-amino-1-phenyl-5-imino-4.S-dihydro-1.2.4-triazole.

As fiber material there are used in the process according to the presentinvention particularly cotton or regenerated cellulose, furthermorewool, silk, acetate rayon, polyamide or poloyvinylalcohol fibers.

The after treatment of the dyeings and printings prepared according toknown methods may be carried out at an elevated temperature, preferablybetween about 80 C. and 100 C. in an aqueous bath, preferably in a bathrendered alkaline with soda, in the presence of dispersing agents ordetergents for example a fatty alcohol polyglycol ether, an alkylphenolpolyglycol ether, an alkylnaphthol polyglycol ether, a fatty acid amidepolyglycol ether, a fatty acid polyglycol ester, condensation productsfrom an aminoalkyl or hydroxyalkylsulfonic acid and a fatty acid of highmolecular weight or alkylarylsulfonates. Alternatively, the dyeings andprintings are first treated in a bath containing a dispersing agent or adetergent, a compound yielding metal, a complex-forming compound and acompound splitting of? alkali, for example, the sodium salt oftrichloroacetic acid and subsequently steamed. During steaming, alkaliis set free and metal complexes are formed.

This method is advantageous where discharge pastes are printed beforesteaming. In other cases, it is unneces sary to add an agent splittingoff alkali and the articles may be treated, before steaming, with asolution giving an alkaline reaction containing a dispersing agent ordetergent, a compound forming metal complexes and a compound yieldingmetal.

As compounds yielding metal there are preferably used the water-solublesalts of copper, nickel or cobalt, for example sulfates, chlorides,bromides, nitrates, acetates, formiates and salts of organic sulfonicacids. Cobalt salts are advantageously used together with an oxidizingagent, for example alkali metal perborates, alkali metal persulfates oralkali metal percarbonates.

As compounds forming complexes which may be used for the process of thepresent invention there may be mentioned more especially: alkali metalphosphates, such as alkali metal metaphosphates, alkali metalpyrophosphates or alkali metal polyphosphates, alkanolamines such asdiethanolamine 'or triethanolamine, aliphatic dicarboxylic acids such asoxalic acid or maleic acid, aliphatic hydroxycarboxylic acids, forexample citric acid, tartaric acid, lactic acid or gluconic acid oraliphatic aminocarboxylic acids such as aminoacetic acid,nitrilotriacetic acid, ethylenediamine tetracetic acid or glutamic acid,the choice of the compounds forming complexes being dependent on thestability of the resulting metal complex compounds to alkali metal.

The process according to the invention is especially advantageous forthe preparation of white and colored discharges whereby the white andcolored discharges are prepared first in the usual manner and thensubjected to the after-treatment according to the invention. By thismethod purer discharges are obtained than with the usual metallizationand subsequent after-treatment with detergents and dispersing agents.

In the process according to the invention wherein the treatment bathcontains a compound yielding metal and a compound forming complexes inaddition to a dispersing agent or detergent, metal complexes are formedmore rapidly and often at lower temperatures than those used in theprocess described in US. Patent No. 2,768,053.

The following examples serve to illustrate the invention but they arenot intended to limit it thereto.

Example 1 A cotton fabric is continuously dyed on the foulard in theusual manner, while intermediately drying the impregnation, with asolution containing per liter of water 6.08 grams of1-(2'.3-hydroxynaphthoylamino) 2 methoxybenzene and a diazo solutioncontaining, per liter of water, 5.4 grams of 1-amino-6-chloroindazole.After passing through air for 30 seconds and through a bath at C.containing, per liter of water, 1 gram of disodium phosphate, thematerial is rinsed and after-treated for 20 minutes at C. to C. at agoods-to-liquor ratio of 1:20 in a bath containing, per liter of water,1 gram of a reaction product from about 10 mols of ethylene oxide and 1mol of isododecyl phenol, 3 grams of sodium carbonate, 0.8 gram ofcobalt chloride, 1.6 grams of aminoacetic acid and 0.08 gram of sodiumperborate. The material is then rinsed and dried. A green dyeing havinggood properties of fastness is obtained.

In order to produce a white discharge, the material is dried afterdevelopment with the diazo solution and the cotton fabric is printedwith a printing paste containing, per kilogoram, 200 grams of sodiumformaldehyde sulfoxylate, 50 grams of the sodium salt ofbenzylsulfanilic acid 1:1, 30 grams of potassium carbonate, 30 grams ofanthraquinone paste of 30% strength, 450 grams of a starch-tragacanththickening, grams of zinc white 1:1 and grams of water.

The material is then dried, steamed, rinsed at 90 C. With a solutioncontaining, per liter of water, 2.2 grams of caustic soda and with hotwater, and then after-treated as described above. A white discharge ongreen base is obtained.

By using vat dyestuffs in the printing paste, there can likewise beproduced color discharges on green base.

By using in this example 0.8 gram of nickel sulfate, instead of 0.8 gramof cobalt chloride, there is obtained a dark violet dyeing or a whitedischarge on dark violet base.

Example 2 A cotton fabric is dyed in the usual manner with a solutioncontaining, per kilogram of goods, 6.3 grams of 1-(2'.3'-hydroxynaphthoylamino)-2.4-dimethoxy-5 chlorobenzene and 4.48 gramsof diazotized 3-amino-6chlorindazole, and treated with a solutioncontaining, per liter of water, 1.5 grams of a reaction product fromabout 6 mols of ethylene oxide and 1 mol of isododecyl phenol, 7.8 gramsof cobalt chloride, 8.75 grams of the sodium salt of nitrilotriaceticacid in the form of its aqueous solution of 25% strength, and 32 gramsof the sodium salt of trichloroacetic acid. The solution is adjusted toa pH of 6.8 by means of 6 grams of trichloroacetic acid.

The cotton fabric is then dried and printed with a printing pastecontaining, per kilogram, 200 grams of sodium formaldehyde sulfoxylate,100 grams of zinc white 1:1, 50 grams of the sodium salt ofbenzylsulfanilic acid, 30 grams of potassium carbonate, 30 grams ofanthraquinone paste of 30% strength, 450 grams of a starchtragacanththickening and 140 grams of water.

The fabric is then dried, steamed for 7 minutes at about 102 C., rinsedfirst at 90 C. with a solution containing, per liter of water, 2.2 gramsof caustic soda, and then several times in the hot and in the cold,soaped with a solution containing, per liter of water, 1 gram of areaction product from about 6 mols of ethylene oxide and 1 mol ofisododecyl phenol, 3 grams of sodium carbonate and 0.5 gram of thesodium salt of nitrilotriacetic acid, rinsed and dried.

A green dyeing with white discharge effects is obtained.

Example 3 A cotton fabric is dyed in the usual manner with a solutioncontaining, per kilogram of goods, 6.45 grams of 1-(6'-methoxy-2'.3-hydroxynaphthoylamino)-2 methoxybenzene and 4.48 gramsof diazotized 3-amino-6-chloroindazole and treated with a solutioncontaining, per liter of water, 8.3 grams of copper sulfate, 9 grams ofthe sodium salt of nitn'lotriacetic acid, 32.5 grams of the .sodium saltof trichloroacetic acid and 1.5 grams of a reaction product from about 6mols of ethylene oxide and 1 mol of isododecyl phenol, this solutionbeing neutralized with 6 grams of trichloroacetic acid.

The material is then dried, steamed for 10 minutes at about 102 C.,soaped at the boil, rinsed and dried. A blue grey dyeing is obtained.

6 Example 4 A cotton fabric is dyed in the usual manner with a solutioncontaining, per kilogram of goods, 7.5 grams of 1-(2'3'-hydroxynaphthoylamino)-2.4-dimethoxy-5 chlorobenzene and 4.1 gramsof diazotized 3-amino-6-chloroindazole and slop-padded with a coldsolution containing, per liter of water, 7.2 grams of cobalt chloride,19.4 grams of aminoacetic acid, grams of urea and 17 cc. of sodiumhydroxide solution of 38 B. and having a pH of 9.6.

The material is then dried and steamed for 7 minutes at 102 C. It isthen rinsed, soaped at the boil and dried.

A green dyeing is obtained.

Example 5 A cotton fabric dyed with the azo-dyestuif mentioned inExample 4 is slop-padded with a cold solution containing, per liter ofwater, 7.5 grams of copper sulfate, 22.5 grams of triethanolamine and 50grams of urea and having a pH of 8.6.

The material is dried and steamed for 7 to 10 minutes at 102 C., rinsedand soaped at the boil.

A blue-grey dyeing is obtained.

Instead of 22.5 grams of triethanolamine, there may also be used in thepresent example 38 grams of an alkaline solution of 25% strength of thesodium salt of nitrilotriacetic acid having a pH of 11.5.

In the following table are given further components which can be used inthe process of this invention and also the tints of the azo-dyestulfscontaining metal produced from these components on the fiber.

Diazo component Coupling component Dispersing agent Metal-yieldingComplex-forming Tint compound compound 2-(2-amino-4'-methoxy-5'-2.3-hydroxy-naphthoyl- Reaction product from 10 Copper sulfate--Triethanolamlne Dark brown.

methylphenylybenztriaminobenzene. mols ethylene oxide and azole-l-oxide.1 mol nonyl phenol. 3-amino-5-chloroindazole.- 1-(2.3-hydroxynaphthoyldodo do Dark bl e,

amino)-4-chlorobenzene. 3-arnlno-6-chl0roindazole.1-(2-hydroxyanthracene-3- do do rlo Gr n,

carboylamlno)-2-rnethylbenzene. Do do do Cobalt chlorlde..Nitrilotrlacetlc acld Do. Do 1-(2.3-hydr0xyn phth v1- do ..-..do Sodiumpolyphosphate.. Do.

amin0)-2-methoxybenzene. D0 1-(2-hydroxycar az0l -3- do Sodiumpyrophosphate-. Grey.

carboylamino)-4-chl0robenzene. I Do 1-(2.3-hydr0xynapht 0y1- ..-.do doCitric acid Green.

amino)-2ethoxybenzene. Do 1-(2'.3'-hydr0xynaphth y1- .do Copper sulfate-Oxalic acid Blue grey,

amino) -2-methoxybenzene. Do 1-(2.3-hydroxynaphthoyld0 d0 Amlnoaceticacid Do.

amino)-2-methylbenzene. D do .do Cobalt chloride. Gluconie acid"-.- DoDo 1-(2.3'-hydroxynaphtho- Reaction product from 6 Copper sulfate Sodiumpyrophosphate. Do.

ylamino)-2.4-dimethoxymols ethylene oxide and 5-chlorobenzene. 1 molnonyl phenol. 3-amlno-l-rnethyl-fi-chlorol-(6-methoxy-2.3-hydr0xdoNickel sulfate... Aminoacetic acid Dark blue.

indazole. ynaphthoylamino)-2-methoxybcnzcne. 3-arnino-1-methyl-5-nitro-2 (2.3-hydroxynaphthodo do do Do.

indazole. ylamino)-naphthalene. l-aminocarbazole 1-(2.3-hydroxynaphtho---do Cobalt chloride. do Black.

ylarnino),2.4-dimethoxy- 5-chlorobenzene. Do do (10 Copper sulfateTriethanolamine Blue black. 7-amino-2j dimethylbenz-1-(2.3-hydroxynaphtl1o- -d0 Nickel sulfate... Aminoacetic acid Claret.

imidazole. ylamino)-2-I.nethyl-4- chlorobenzene.7-arnino-5-methylbcnztri- 2-(2.3-hydroxynaphthc- -.do Copper sulfateTriethanolamine Currant.

azole. ylamino)-3-methoxydiphenylene oxide. S-aminoquinoline2.3-hydroxynaphthoyl- ..do .do Claret.

amlnobenzene. Do do Reaction product from 20 Cobalt chloride.Amlnoacetic acid Garnet.

mols ethylene oxide and 1 mol octadecyl alcohol. Do do Reaction productfrom 20 Nickel sulfate... do Claret.

mols ethylene oxide and 1 mol oleyl alcohol. 2-(2-amlno4-methoxy-5-2-(2.3-hydroxynaphthoyl- Reaction product from 10 Copper sulfate...Tartarlc acid Dark brown.

methylphenyD-benztriaamino)-naphthalene. mols ethylene oxide andzole-l-oxide. 1 mol nonyl phenol. 2-(2-amino-4.5'-diethoxy-'1-(2.3-hydroxynaphthoy1- ..do Copper nitrate" Diethanolamine Do.

phenyD-(i-methoxybenzamino) -4-chlorobenzene. triazole-l-oxide.

Do 1-(2.3-hydroxynaphthoyl- Reaction product from 6 Copper acetate"Tricthanolamine Do.

amino)-3-nitrobenzene. mols ethylene oxide and 1 mol nonyl phenol.

Diazo component Coupling component Disperslng agent Metal-yieldingComplex-forming Tint compound compound 2-(2'-amino-4.5'-diethoxy-2-(2.3-hydrozwnaphthoyl- Reaction product from 6 Copper acetatc..Trlethanolamine Dark brown.

phenyD-fi-methoxybenzamino)-naphtl1alene. mols etylene oxide andtriazole. 1 mol nonyl phenol. l-rncthyl-5-(2'-amino-5'-1-(2.3-hydroxynaphthoyl- Reaction product from 20 Cobalt sultate.Nitrilotriacetic acid Yellow brown.

chloropheny1)-1,2,3,4- amino)-2-methoxybenzene. mols ethylene oxide andtetrazole. 1 mol oleyl alcohol.

Do l-(2.3-hydroxynaphthoyl- Reaction product from 10 Nickel sulfate...Aminoacetic acid Red brown.

amino)-2-methyl-4-memols ethylene oxide and thoxybenzene. 1 mol nonylphenol. 2 (2-arnino-4'-chloro- 2.3-hydroxynaphthoyl- Reaction productfrom 12 do ..do Garnet,

phenyll-LS-diphenylaminobenzene. mols ethylene oxide and 1.3.4-triazole.1 mol dodecyl phenol. 2(2-amino-5-chlcro- 1-(2.3-hydroxynaphthoyl-Reaction product from 40 Cobalt chloride. Nitrllotriacetic acid Redbrown.

phenyl)'5-phcnyl-1.3.4- amino)-2.4-dimethoxy-5- mols ethylene oxide andoxdiazole. chlorobenzene. 1 mol castor oil. 2-(2-aminophenyl)-1.5-1-(2.3 hydroxynaphthoyh Reaction product from 6 Copper suliate.-Triethanolamine Brown.

dimethylbenzlmidazole. amino)-2.5-dixnethoxy-4- mols ethylene oxide andchlorobenzene. 1 mol isododecyl phenol. Do 1-(2.3-hydroxynaphthoyl-Reaction product from 9 Nickel sulfate... Aminoacetic acid Garnet.

urnino)-2.4-dimethoxy-5- mols ethylene oxide and chlorobenzene. 1 molhexyl heptyl B- naphthol. 2-(2-aminophenyl)-5-1-(2.3'-liydroxynaphthoyl- Reaction product from 10 Copper sulfateTriethanolamlne Rust red.

chlorobenzthiazole. amino)-2-methyl-4-memols ethylene oxide andthoxybenzene. 1 mol uonyl phenol.

We claim: low aliphatic carboxylic acids, and (c) a metal complex 1. Analkaline composition suitable for the after-treatment of vegetablefibres which have been dyed with a 2 water-insoluble azo-dyestutf havinga grouping selected from the group consisting of H N N and wherein Arepresents a heterocyclic ring having from 5 to 6 ring atoms, consistingessentially of (a) a non-ionic dispersing agent selected from the groupconsisting of fatty alcohol polyglycol ethers, alkyl phenol polyglycolethers, alkyl naphthol polyglycol cthers, fatty acid polyaliphatic aminocarboxylic acids.

forming compound selected from the group consisting of alkali metalphosphates, hydroxyalkylamines, aliphatic dicarboxylic acids, aliphatichydroxycarboxylic acids and 2. The process for the production of complexmetal compounds having a metal selected from the group con- 50 sistingof copper, cobalt and nickel, of a water-insoluble azo-dyestufi having agrouping selected from the group consisting of wherein A represents aheterocyclic ring having from 5 to 6 ring atoms, on vegetable fibres,which comprises aftertreating vegetable fibres, which have been dyedwith a glycol esters and fatty acid amide polyglycol others, (11) ametal yielding agent selected from the group consisting of the copper,cobalt and nickel salts of the inorganic and water-insolubleazo-dyestuif having one of said four groupings, with an alkalinecomposition consisting of (a) a non-ionic dispersing agent selected fromthe group consisting of fatty alcohol polyglycol ethers, alkyl phenolpolyglycol ethers, alkyl naphthol polyglycol ethers, fatty 5 acidpolyglycol esters and fatty acid amide polyglycol ethers, (b) a metalyielding agent selected from the group consisting of the copper, cobaltand nickel salts of the inorganic and low aliphatic carboxylic acids,and (c) a metal complex forming compound selected from the groupconsisting of alkali metal phosphates, hydroxyalkylamines, aliphaticdicarboxylic acids, aliphatic hydroxycarboxylic acids and aliphaticamino carboxylic acids.

10 3. The process of claim 2, wherein the treatment of the coloredvegetable fibres with said alkaline composition is carried out at atemperature in the range of about 80 C. to 100 C.

References Cited in the file of this patent UNITED STATES PATENTS StreckOct. 23, 1956 Streck July 7, 1959

2. THE PROCESS FOR THE PRODUCTION OF COMPLEX METAL COMPOUNDS HAVING AMETAL SELECTED FROM THE GROUP CONSISTING OF COPPER, COBALT AND NICKEL,OF A WATER-INSOLUBLE AZO-DYESTUFF HAVING A GROUPING SELECTED FROM THEGROUP CONSISTING OF